Fluorescent Dye/Nickel Synergistic Catalytic Decarboxylative Carbonylation Reaction

Weiguo Yu, Lingna Wang, Xiaocong Yu, Shuping Luo
2022 Youji huaxue  
The decarboxylative carbonylation of α-amino acids was carried out with N-benzoyl succinimide as the carbonylation reagent under the synergistic catalysis of fluorescent dye/nickel catalysts. In this reaction, 16 kinds of α-amino ketone-containing derivatives were synthesized with good yields (up to 78%), and the light conversion efficiency was up to 3.25×10 -1 mmol/(kW•h). In addition, the possible mechanism of the photocatalytic reaction was proposed: α-amino carboxylic acid was catalyzed by
more » ... isible light to form α-amino alkyl radicals, which entered the nickel catalytic cycle and produced α-amino ketone target compound via oxidation addition and reduction elimination process. The reactions could generate a variety of α-amino ketones with broad substrate scope under mild conditions and might have widespread use in synthesis of α-amino ketone-containing drug molecules and peptide modifications. Keywords photocatalysis; nickel catalysis; single electron transfer; decarboxylative coupling reaction α-氨基酮是有机合成化学和药物化学中非常重要 的支架, 它们存在于许多生物活性天然产物和药物制剂 中 [1] , 例如含有手性 α-氨基酮结构的天然产物卡西酮, 它是从阿拉伯茶中分离出的单胺生物碱 [2] , 含有 α-氨基 酮结构的药物化合物包括用作麻醉剂的氯胺酮 [3] 、用作 治疗抑郁症的安非他酮和治疗心脑血管疾病的普拉格 雷(图 1) [1a,4] , 因此如何制备 α-氨基酮的方法被广泛研究. α-氨基酮合成的传统方法有 α-酮亚胺的氢化反应、 烯醛和亚胺的交叉偶联反应、烯烃和烯醇醚的氨化反应 以及一些以酮作为反应前体的合成方法. Sun 等 [5] 开发 了氮杂环卡宾(NHC)催化的烯醛和活化的酮亚胺的对映 选择性氮杂安息香反应. Wen 等 [6] 发现通过布朗斯特酸 催化 α-酮亚胺进行高效地区域选择性和对映选择性转 移氢化和二酮的还原胺化, 以高收率(最高>99%)、 优异 的区域选择性(最高>99∶1)和对映选择性(最高 98% ee 值)制备了一系列手性 α-氨基酮. Prasad 等 [7] 通过由 N-
doi:10.6023/cjoc202110018 fatcat:gz2hsu2wmresvcql3b454dlgsa